The importance of atmospheric input of terrestrial organic material to deep sea sediments

The concentrations of lipids were determined in atmospheric particle, gas and rain samples collected from the tropical North Pacific to assess lipid sources, transport mechanisms and fluxes to the ocean surface. Four lipid compound classes (aliphatic hydrocarbons, fatty alcohols, fatty acid esters, and salts) all unequivocally show a terrestrial vascular plant source. These aerosol lipids originate from wind erosion of Asian and American soils and direct emission from vegetation. The major fluxes result from rain rather than dry deposition. These fluxes are large enough to have a major potential impact on the inventory of terrestrially derived lipid material found in deep-sea sediments. This has been showm for n-alkanes, fatty alcohols, fatty acids, total lipids and for organic carbon. By comparing atmospheric and sediment trap fluxes with sediment accumulation rates, it is suggested that some biogenic terrestrial material is more protected from degradation than marine-derived material.     

Characteristics of hydrothermal plumes from two vent fields on the Juan de Fuca Ridge, northeast Pacific Ocean

Deep CTD/transmissometer tows and water bottle sampling were used during 1985 to map the regional distribution of the neutrally-buoyant plumes emanating from each of two major vent fields on the Southern Symmetrical Segment (SSS) and Endeavour Segment (ES) of the Juan de Fuca Ridge. At both vent fields, emissions from point and diffuse hydrothermal sources coalesced into a single 200-m-thick plume elongated in the direction of current flow and with characteristic temperature anomalies of 0.02–0.05°C and light-attenuation anomalies of 0.01–0.08 m⁻¹ (10–80 μg/l above background). Temperature anomalies in the core of each plume were uniform as far downcurrent as the plumes were mapped (10–15 km). Downcurrent light-attenuation trends were non-uniform and differed between plumes, apparently because different vent fluid chemistries at each field cause significant differences in the settling characteristics of the hydrothermal precipitates. Vent fluids from the SSS are metal-dominated and mostly precipitate very fine-grained hydrous Fe-oxides that remain suspended in the plume. Vent fluids from the ES are sulfur-dominated and precipitate a high proportion of coarser-grained Fe-sulfides that rapidly settle from the plume. The integrated flux of each vent field was estimated from measurements of the advective transport of each plume. Heat flux was 1700 ± 1100 MW from the ES and 580 ± 351 MW from the SSS. Particle flux varied from 546 ± 312 g/s to 204 ± 116 g/s at the ES depending on distance from the vent field, and was 92 ± 48 g/s from the SSS.     

Lead in corals: reconstruction of historical industrial fluxes to the surface ocean

Twentieth century environmental lead chronologies for the western North Atlantic, Pacific, and Indian Oceans have been reconstructed from annually-banded scleractinian corals. Measurements of lattice-bound Pb in sequential coral bands reveal temporal changes in surface water Pb concentrations and Pb isotopic distributions. Perturbations are observable in all specimens studied, attesting to global augmentation of environmental Pb by industrialization.In the western North Atlantic, Pb perturbations have occurred in direct response to the American industrial revolution and the subsequent introduction and phasing-out of alkyl Pb additives in gasoline. Surface ocean conditions near Bermuda may be reliably reconstructed from the coral data via a lead distribution coefficient of 2.3 for the species,Diploria strigosa. Based on²¹⁰Pb measurements, a similar distribution coefficient may be characteristic of corals in general. Surface Pb concentrations in the pre-industrial Sargasso Sea were about 15–20 pM. Concentrations rose to near 90 pM by 1923 as a result of metals manufacture and fossil fuel combustion. Beginning in the late 1940's, increased utilization of leaded gasoline eventually led to a peak concentration of 240 pM in 1971, representing an approximate 15-fold increase over background. Surface ocean concentrations are presently declining rapidly (128 pM in 1984) as a result of curtailed alkyl Pb usage. Lead isotopic shifts parallel the concentration record indicating that characteristic industrial and alkyl Pb source signatures have not changed appreciably in time. Industrial releases recorded in the Florida Keys reflect a weaker source and evidence of recirculated Pb (5–6 years old) from the North Atlantic subtropical gyre. An inferred background concentration of 38 pM suggests influence of shelf and/or resuspended inputs of Pb to these coastal waters.In remote areas of the South Pacific and Indian Oceans, industrial signals are fainter and the corals studied much younger than their Atlantic counterparts. Contemporary Pb concentrations implied by coral measurements (assumingK_D = 2.3) are 40–50 pM for surface waters near Tutuila and Galapagos in the South Pacific, and 25–29 pM near Mauritius in the Indian Ocean. A single coral band from Fiji (1920 ± 5yr) implies a pre-industrial surface water concentration of 16–19 pM Pb for the South Pacific. In view of reported surface water measurements and the North Atlantic coral data, the Pacific coral extrapolations may be slightly high. This could be a result of small variations inK_D among different coral genera, or incorporation of diagenetic Pb by corals sampled in coastal environments.     

Sorption of noble gases by solids,with reference to meteorites. I. Magnetite and carbon

To simulate trapping of meteoritic noble gases by solids, 18 samples of Fe₃O₄ were synthesized in a noble gas atmosphere at 350–720 K by the reactions: 3Fe + 4H₂O → Fe₃O₄ + 4H₂ (Ne, Ar, Kr, Xe) 3Fe + 4CO → Fe₃O₃ + 4C + carbides (Xe only) Phases were separated by selective solvents (HgCl₂, HCl). Noble gas contents were analyzed by mass spectrometry, or, in runs where 36 d Xe¹²⁷ tracer was used, by γ-counting. Surface areas, as measured by the BET method, ranged from 1 to 400 m²/g. Isotopic fractionations were below the detection limit of 0.5%/m.u.Sorption of Xe on Fe₃O₄ and C obeys Henry's Law between $\text{1 × 10}{}^{\mathrm{?8}}$ and $\text{4 × 10}{}^{\mathrm{?5}}$ atm, but shows only a slight temperature dependence between 650 and 720 K ($\text{ΔH}{}_{\mathrm{sol}}\text{= ?4 ± 2}\text{kcal/mole}$). The mean distribution coefficient K_Xe is $\text{0.28 ± 0.09}$ cc STP/g atm for Fe₃O₄ and only a factor of $\text{1.2 ± 0.4}$ greater for C; such similarity for two cogenetic phases was predicted by Lewis et al. (1977). Stepped heating and etching experiments show that 20–50% of the total Xe is physically adsorbed and about 20% is trapped in the solid. The rest is chemisorbed with $\text{ΔH}{}_{\mathrm{s}}\text{? ?13}\text{kcal/mole}$. The desorption or exchange half-time for the last two components is >10² yr at room temperature.Etching experiments showed a possible analogy to “Phase $\text{Q}$” in meteorites. A typical carbon + carbide sample, when etched with HNO₃, lost 47% of its Xe but only 0.9% of its mass, corresponding to a ~0.6 Å layer. Though this etchable, surficial gas component was more thermolabile than $\text{Q}$ (release $\text{T}$ below 1000°C, compared to 1200–1600°C), another experiment shows that the proportion of chemisorbed Xe increases upon moderate heating (1 hr at 450°C). Apparently adsorbed gases can become “fixed” to the crystal, by processes not involving volume diffusion (recrystallization, chemical reaction, migration to traps, etc.). Such mechanisms may have acted in the solar nebula, to strengthen the binding of adsorbed gases.Adsorbed atmospheric noble gases are present in all samples, and dominate whenever the noble gas partial pressure in the atmosphere is greater than that in the synthesis. Many of the results of Lancet and Anders (1973) seem to have been dominated by such an atmospheric component; others are suspect for other reasons, whereas still others seem reliable. When the doubtful samples of Lancet and Anders are eliminated or corrected, the fractionation pattern—as in our samples—no longer peaks at Ar, but rises monotonically from Ne to Xe. No clear evidence remains for the strong temperature dependence claimed by these authors.     

Sorption of noble gases by solids,with reference to meteorites. III. Sulfides,spinels, and other substances; on the origin of planetary gases

To simulate trapping of noble gases by meteorites, we reacted 15 FeCr or FeCrNi alloy samples with CO, H₂O or H₂S at 350–720 K, in the presence of noble gases. The reaction products, including (Fe,Cr)₂O₃, FeCr₂S₄, FeS, C, and Fe₃C, were analyzed by mass spectrometry, usually after chemical separation by selective solvents. Three carbon samples were prepared by catalytic decomposition of CO or by dehydration of carbohydrates with H₂SO₄.The spinel and carbon samples were similar to those of earlier studies (Yang et al., 1982 and Yang and Anders, 1982), with only minor effects attributable to the presence of Ni. All samples sorted substantial amounts of noble gases, with distribution coefficients of 10^?1–10^?2 cm³ STP/g atm for Xe. On the basis of release temperature three gas components were distinguished: a generally dominant physisorbed component (20–80% of total), and two more strongly bound, chemisorbed and trapped components. Judging from the elemental pattern, the adsorbed components were acquired at the highest noble gas partial pressure encountered by the sample—atmosphere or synthesis vessel.Sulfides, particularly daubréelite, showed three distinctive trends relative to chromite or magnetite: the high-T component was larger, 30–70% of the total; $\text{Ne}\text{Xe}$ ratios were higher, by up to 10², possibly due to preferential diffusion of Ne during synthesis. In one synthesis, at relatively high P, the gases were sorbed with only minimal elemental fractionation, presumably by occlusion.Most of the features of primordial noble gases can be explained in terms of the data and concepts presented in the three papers of this series. The elemental fractionation pattern of Ar, Kr, Xe in meteorites, terrestrial rocks, and planets resembles the adsorption pattern on the solids studied: carbon, spinels, Sulfides, etc. The variation in $\text{Ne}\text{Ar}$ ratio may be explained by preferential diffusion of Ne. The high release temperature of meteoritic noble gases may be explained by transformation of physisorbed to chemisorbed gas, as observed in some experiments. The ready loss of meteoritic heavy gases on surficial oxidation (“Phase Q”) is consistent with adsorption, as is the high abundance. Extrapolation of the limited laboratory data suggests that the observed amounts of noble gases could have been adsorbed from a solar gas at 160–170 K and 10^?6–10^?5 atm, i.e. in the early contraction stages of the solar nebula. The principal unsolved problem is the origin of isotopically anomalous, apparently mass-fractionated noble gases in the Earth's atmosphere and in meteoritic carbon and chromite.     

Are C1 chondrites chemically fractionated? a trace element study

Six C1 chondrite samples and a C2 xenolith from the Plainview H5 chondrite were analyzed by radiochemical neutron activation for the elements Ag, Au, Bi, Br, Cd, Ce, Cs, Eu, Ge, In, Ir, Lu, Nd, Ni, Os, Pd, Pt, Rb, Re, Sb, Se, Sn, Tb, Te, Tl, Yb, and Zn. The data were combined with 9 earlier analyses from this laboratory and examined for evidence of chemical fractionation in C1 chondrites.A number of elements (Br, Rb, Cs, Au, Re, Os, Ni, Pd, Sb, Bi, In, Te) show small but correlated variations. Those of the first 8 probably reflect hydrothermal alteration in the meteorite parent body, whereas those of Sb, Bi, In, and Te may at least in part involve nebular processes. Br and Au show systematic abundance differences from meteorite to meteorite, which suggests hydrothermal transport on a kilometer scale. The remaining elements vary from sample to sample, suggesting transport on a centimeter scale.There is no conclusive evidence for nebular fractionation affecting C1 's. Though C1 chondrites have lower $\text{Zr}\text{Hf}$ and $\text{Ir}\text{Re}$ ratios than do other chondrite classes, these ratios vary in other classes, suggesting that those classes rather than C1's are fractionated. Three fractionation-prone REE—Ce, Eu, and Yb have essentially the same relative abundances in C1's and all other chondrite classes, and hence apparently are not fractionated in C1's. We did not confirm the large Tb and Yb variations in C1's reported by other workers.We present revised mean C1 abundances for 35 elements, based on the new data and a critical selection of literature data. Changes are generally less than 10%, except for Br, Rb, Ag, Sb, Te, Au, and the REE.The Plainview C2 xenolith has normal trace element abundances, except for 3 elements falling appreciably above the C2 range: Rb, Cs, and Bi. Hydrothermal alteration may be the reason for all 3, though nebular fractionation remains a possibility for Bi.     

Uranium and thorium isotope concentrations in foraminiferal calcite

Uranium and thorium isotope activities were measured by isotope dilution alpha spectrometry in four late Pleistocene and Holocene foraminiferal calcite samples. Sample cleaning methods were utilized to separate calcite tests from contaminating clay and surface oxide coatings. The maximum concentration of lattice bound uranium is 0.023 ppm (10 × 10^?9 moles U/mole Ca), consistent with the lowest reported value, 0.025 ppm [1].²³⁰Th/²³⁴U activity ratios in samples cleaned as described above are much greater than one, indicating that the cleaning methods used do not effectively remove²³⁰Th from the surfaces of the calcite. The upper limit for lattice bound²³²Th is 0.039 ppm (17 × 10^?9 moles Th/mole Ca).